3.3 Kierlik and Rosinberg........................... 66
3.4 Segura, Chapman and Shukla...................... 68
3.5 Yu and Wu................................ 71
3.6 Tripathi, Dominik and Chapman . ................... 74
3.7 Conclusions................................ 77
4 Modified iSAFT: a new density functional theory for inhomogenous
polymers 81
4.1 Introduction................................ . 82
4.2 Model and theory............................. 84
4.2.1 Free energies ........................... 86
4.2.2 Functional derivatives of free energies......... 89
4.2.3 Equilibrium density profile................ 92
4.3 Results and discussion.......................... 95
4.3.1 Ideal chains............................ 96
4.3.2 Lipids............................... 97
4.3.3 Block Copolymers......................... 103
4.4 Conclusions................................ 108
5 Modified iSAFT: Application to symmetric diblock copolymers 112
5.1 Introduction................................ 112
5.2 Model system and theory......................... 118
5.3 Results and discussion.......................... 123
5.3.1 Bulk diblock copolymer melts.................. 124
5.3.2 Confined diblock copolymer ultra-thin films .......... 128
5.4 Conclusions................................ 138
6 Modified iSAFT: Application to grafted polymer chains 142
6.1 Introduction................................ 143
6.2 Extension of modified iSAFT to grafted polymer chains........ 150
6.3 Results and discussion................. 155
6.3.1 Structure of polymer brush in the absence of free polymer solvent 155
6.3.2 Structure of polymer brushes in the presence of an explicit solvent 161
6.3.3 Interaction between two grafted monolayers in the absence of
free polymer............................ 163
6.3.4 Interaction between two grafted monolayers in the presence of
free polymer............................ 166
6.4 Conclusions................................ 173
7 Modified iSAFT: Extension to inhomogenous branched polymers 180
7.1 Introduction................................ 180
7.2 Model and theory............................. 183
7.2.1 Application to star like branched polymers........... 195
vi
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